Method of Preparing a Material of a Battery Cell

ABSTRACT

A continuous process for producing a material of a battery cell using a system having a mist generator, a drying chamber, one or more gas-solid separators and a reactor is provided. A mist generated from a liquid mixture of two or more metal precursor compounds in desired ratio is dried inside the drying chamber. Heated air or gas is served as the gas source for forming various gas-solid mixtures and as the energy source for reactions inside the drying chamber and the reactor. One or more gas-solid separators are used in the system to separate gas-solid mixtures from the drying chamber into solid particles mixed with the metal precursor compounds and continuously deliver the solid particles into the reactor for further reaction to obtain final solid material particles with desired crystal structure, particle size, and morphology.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/747,450 filed on Jan. 20, 2020, which is a continuation of U.S.patent application Ser. No. 16/114,114 filed on Aug. 27, 2018, which isa continuation of U.S. patent application Ser. No. 13/900,915, filed May23, 2013, which claims benefit of U.S. provisional patent applicationSer. No. 61/855,063, filed May 6, 2013. All of the above-referencedapplications are herein incorporated by reference.

FIELD OF THE INVENTION

This invention generally relates to the preparation of materials forbattery applications. More specifically, the invention related to methodand system in manufacturing structured cathode or anode active materialsfor use in secondary batteries.

BACKGROUND OF THE INVENTION

Great efforts have been devoted to the development of advancedelectrochemical battery cells to meet the growing demand of variousconsumer electronics, electrical vehicles and grid energy storageapplications in terms of high energy density, high power performance,high capacity, long cycle life, low cost and excellent safety. In mostcases, it is desirable for a battery to be miniaturized, light-weightedand rechargeable (thus reusable) to save space and material resources.

In an electrochemically active battery cell, a cathode and an anode areimmersed in an electrolyte and electronically separated by a separator.The separator is typically made of porous polymer membrane materialssuch that metal ions released from the electrodes into the electrolytecan diffuse through the pores of the separator and migrate between thecathode and the anode during battery charge and discharge. The type of abattery cell is usually named from the metal ions that are transportedbetween its cathode and anode electrodes. Various rechargeable secondarybatteries, such as nickel cadmium battery, nickel-metal hydride battery,lead acid battery, lithium ion battery, and lithium ion polymer battery,etc., have been developed commercially over the years. To be usedcommercially, a rechargeable secondary battery is required to be of highenergy density, high power density and safe. However, there is atrade-off between energy density and power density.

Lithium ion battery is a secondary battery which was developed in theearly 1990s. As compared to other secondary batteries, it has theadvantages of high energy density, long cycle life, no memory effect,low self-discharge rate and environmentally benign. Lithium ion batteryrapidly gained acceptance and dominated the commercial secondary batterymarket. However, the cost for commercially manufacturing various lithiumbattery materials is considerably higher than other types of secondarybatteries.

In a lithium ion battery, the electrolyte mainly consists of lithiumsalts (e.g., LiPF6, LiBF4 or LiClO4) in an organic solvent (e.g.,ethylene carbonate, dimethyl carbonate, and diethyl carbonate) such thatlithium ions can move freely therein. In general, aluminum foil (e.g.,15˜20 μm in thickness) and copper foil (e.g., 8˜15 μm in thickness) areused as the current collectors of the cathode electrode and the anodeelectrode, respectively. For the anode, micron-sized graphite (having areversible capacity around 330 mAh/g) is often used as the activematerial coated on the anode current collector. Graphite materials areoften prepared from solid-state processes, such as grinding andpyrolysis at extreme high temperature without oxygen (e.g.,graphitization at around 3000° C.). As for the active cathode materials,various solid materials of different crystal structures and capacitieshave been developed over the years. Examples of good cathode activematerials include nanometer- or micron-sized lithium transition metaloxide materials and lithium ion phosphate, etc.

Cathode active materials are the most expensive component in a lithiumion battery and, to a relatively large extent, determines the energydensity, cycle life, manufacturing cost and safety of a lithium batterycell. When lithium battery was first commercialized, lithium cobaltoxide (LiCoO₂) material is used as the cathode material and it stillholds a significant market share in the cathode active material market.However, cobalt is toxic and expensive. Other lithium transition metaloxide materials, such as layered structured LiMeO₂ (where the metalMe=Ni, Mn, Co, etc.; e.g., LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂, with theirreversible/practical capacity at around 140˜150 mAh/g), spinelstructured LiMn₂O₄ (with reversible/practical capacity at around 110˜120mAh/g), and olivine-type lithium metal phosphates (e.g., LiFePO₄, withreversible/practical capacity at around 140˜150 mAh/g) have recentlybeen developed as active cathode materials. When used as cathodematerials, the spinel structured LiMn₂O₄ materials exhibit poor batterycycle life and the olivine-type LiFePO₄ materials suffer from low energydensity and poor low temperature performance. As for LiMeO₂ materials,even though their electrochemical performance is better, priormanufacturing processes for LiMeO₂ can obtain mostly agglomerates, suchthat the electrode density for most LiMeO₂ materials is lower ascompared to CO₂. In any case, prior processes for manufacturingmaterials for battery applications, especially cathode active materials,are too costly as most processes consumes too much time and energy, andstill the qualities of prior materials are inconsistent andmanufacturing yields are low.

Conventional material manufacturing processes such as solid-statereaction (e.g., mixing solid precursors and then calcination) andwet-chemistry processes (e.g., treating precursors in solution throughco-precipitation, sol-gel, or hydrothermal reaction, etc., and thenmixing and calcination) have notable challenges in generating nano- andmicron-structured materials. It is difficult to consistently produceuniform solid materials (i.e., particles and powders) at desiredparticle sizes, morphology, crystal structures, particle shape, and evenstoichiometry. Most conventional solid-state reactions require longcalcination time (e.g., 4-20 hours) and additional annealing process forcomplete reaction, homogeneity, and grain growth. For example, spinelstructured LiMn₂O₄ and olivine-type LiFePO₄ materials manufactured bysolid-state reactions require at least several hours of calcination,plus a separate post-heating annealing process (e.g., for 24 hours), andstill showing poor quality consistency. One intrinsic problem withsolid-state reaction is the presence of temperature and chemical (suchas O₂) gradients inside a calcination furnace, which limits theperformance, consistency and overall quality of the final products.

On the other hand, wet chemistry processes performed at low temperatureusually involve faster chemical reactions, but a separate hightemperature calcination process and even additional annealing processare still required afterward. In addition, chemical additives, gelationagents, and surfactants required in a wet chemistry process will add tothe material manufacturing cost (in buying additional chemicals andadjusting specific process sequence, rate, pH, and temperature) and mayinterfere with the final composition of the as-produced active materials(thus often requiring additional steps in removing unwanted chemicals orfiltering products). Moreover, the sizes of the primary particles of theproduct powders produced by wet chemistry are very small, and tends toagglomerates into undesirable large sized secondary particles, thusaffecting energy packing density. Also, the morphologies of theas-produced powder particles often exhibit undesirable amorphousaggregates, porous agglomerates, wires, rods, flakes, etc. Uniformparticle sizes and shapes allowing for high packing density aredesirable.

The synthesis of lithium cobalt oxide (LiCoO₂) materials is relativelysimple and includes mixing a lithium salt (e.g., lithium hydroxide(LiOH) or lithium carbonate (Li₂CO₃)) with cobalt oxide (Co₃O₄) ofdesired particle size and then calcination in a furnace at a very hightemperature for a long time (e.g., 20 hours at 900° C.) to make surethat lithium metal is diffused into the crystal structure of cobaltoxide to form proper final product of layered crystal structured LiCoO₂powders. This approach does not work for LiMeO₂ since transition metalslike Ni, Mn, and Co does not diffuse well into each other to formuniformly mixed transition metal layers if directly mixing and reacting(solid-state calcination) their transition metal oxides or salts.Therefore, conventional LiMeO₂ manufacturing processes requires buyingor preparing transitional metal hydroxide precursor compounds (e.g.,Me(OH)₂, Me=Ni, Mn, Co, etc.) from a co-precipitation wet chemistryprocess prior to making final active cathode materials (e.g., lithiumNiMnCo transitional metal oxide (LiMeO₂)).

Since the water solubility of these Ni(OH)₂, Co(OH)₂, and Mn(OH)₂precursor compounds are different and they normally precipitate atdifferent concentrations, the pH of a mixed solution of these precursorcompounds has to be controlled and ammonia (NH₃) or other additives hasto be added slowly and in small aliquots to make sure nickel (Ni),manganese (Mn), and cobalt (Co) can co-precipitate together to formmicron-sized nickel-manganese-cobalt hydroxide (NMC(OH)₂) secondaryparticles. Such co-precipitated NMC(OH)₂ secondary particles are oftenagglomerates of nanometer-sized primary particles. Therefore, the finallithium NMC transitional metal oxide (LiMe₂) made from NMC(OH)₂precursor compounds are also agglomerates. These agglomerates are proneto break under high pressure during electrode calendaring step and beingcoated onto a current collector foil. Thus, when these lithium NMCtransitional metal oxide materials are used as cathode active materials,relatively low pressure has to be used in calendaring step, and furtherlimiting the electrode density of a manufactured cathode.

In conventional manufacturing process for LiMeO₂ active cathodematerials, precursor compounds such as lithium hydroxide (LiOH) andtransitional metal hydroxide (Me(OH)₂ are mixed uniformly insolid-states and stored in thick Al₂O₃ crucibles. Then, the cruciblesare placed in a heated furnace with 5-10° C./min temperature ramp upspeed until reaching 900° to 950° C. and calcinated for 10 to 20 hours.Since the precursor compounds are heated under high temperature for along time, the neighboring particles are sintered together, andtherefore, a pulverization step is often required after calcination.Thus, particles of unwanted sizes have to be screened out afterpulverization, further lowering down the overall yield. The hightemperature and long reaction time also lead to vaporization of lithiummetals, and typically requiring as great as 10% extra amount of lithiumprecursor compound being added during calcination to make sure the finalproduct has the correct lithium/transition metal ratio. Overall, theprocess time for such a multi-step batch manufacturing process will takeup to a week so it is very labor intensive and energy consuming. Batchprocess also increases the chance of introducing impurity with poorrun-to-run quality consistency and low overall yield.

Thus, there is a need for an improved process and system to manufacturehigh quality, structured active materials for a battery cell.

SUMMARY OF THE INVENTION

This invention generally relate to preparing materials for batteryapplications. More specifically, the invention related to method andsystem for producing material particles (e.g., active electrodematerials, etc) in desirable crystal structures, sizes and morphologies.

In one embodiment, a method of producing a material (e.g., cathode oranode active materials) for a battery electrochemical cell is provided.The method includes forming a liquid mixture from two or moreprecursors, flowing a first flow of a first gas that is heated to afirst temperature into a drying chamber, and generating a mist of theliquid mixture at desired liquid droplet sizes inside the dryingchamber, drying the mist of the liquid mixture for a first residencetime inside the drying chamber, and forming a first gas-solid mixtureinside the drying chamber from the heated first gas and the mist. Themethod further includes delivering the first gas-solid mixture out ofthe drying chamber, separating the first gas-solid mixture into a firsttype of solid particles and a waste product, delivering the first typeof solid particles into a reactor, flowing a second flow of a second gasthat is heated to a second temperature inside the reactor, forming asecond gas-solid mixture inside the reactor from the heated second gasand the first type of solid particles, reacting the second gas-solidmixture inside the reactor for a second residence time, oxidizing thesecond gas-solid mixture into an oxidized reaction product, anddelivering the oxidized reaction product out of the reactor. Then, theoxidized reaction product is cooled to obtain a second type of solidparticles.

In one aspect, the second type of solid particles is suitable as anactive electrode material to be further processed into an electrode of abattery cell. In another aspect, the oxidized reaction product isfurther separated into the second type of solid particles and a gaseousside product. In still another aspect, one or more flows of a coolingfluid (e.g., gas or liquid) can be used to cool the temperature of thesecond type of solid particles.

In another embodiment, a method is provided to prepare a material for abattery electrochemical cell, and includes delivering a liquid mixtureinto a process system. The process system includes a drying chamber, amist generator, one or more gas-solid separators; and a reactor. Themethod further includes flowing a first flow of a first gas into thedrying chamber of the process system, generating a mist of desiredliquid droplet sizes from the liquid mixture inside the drying chamberusing the mist generator, drying the mist of the liquid mixture for afirst residence time inside the drying chamber, forming a firstgas-solid mixture inside the drying chamber from the first gas and themist, and separating a chamber product from the drying chamber into afirst type of solid particles and a waste product using the firstgas-solid separator of the process system. Next, the first type of solidparticles is delivered into the reactor of the process system, a secondflow of a second gas heated to a reaction temperature is flowed insidethe reactor, and a second gas-solid mixture is formed inside the reactorfrom the heated second gas and the first type of solid particles. Themethod further includes reacting the second gas-solid mixture inside thereactor for a second residence time, oxidizing the second gas-solidmixture into an oxidized reaction product, and delivering the oxidizedreaction product out of the reactor. In addition the oxidized reactionproduct is separated into a second type of solid particles and a gaseousside product using a second gas-solid separator of the process system.

In still another embodiment, a method is provided to produce anelectrode material and includes forming a liquid mixture from two ormore metal-containing precursors, flowing a first flow of a first gasinto a drying chamber, generating a mist of the liquid mixture insidethe drying chamber, drying the mist for a first residence time insidethe drying chamber, forming a first gas-solid mixture inside the dryingchamber, separating the first gas-solid mixture into a first type ofsolid particles and a waste product, and delivering the first type ofsolid particles into a reactor. Then, a second flow of a second gasheated to a reaction temperature is flowed inside the reactor to form asecond gas-solid mixture with the first type of solid particles. Thesecond gas-solid mixture is reacted for a second residence time into anoxidized reaction product inside the reactor. The oxidized reactionproduct is then separated into a second type of solid particles and agaseous side product, and the second type of solid particles is cooleddown to room temperature and obtained as the material for the batterycell.

In yet another embodiment, a process system for manufacturing a materialof a battery cell is provided. The system includes a mist generatoradapted to generate a mist from a liquid mixture, a drying chamberhaving a chamber inlet and a chamber outlet, and a first gas lineconnected to the drying chamber and adapted to flow a first gas into thedrying chamber and form a first gas-solid mixture inside the dryingchamber. The system further includes a first gas-solid separator and areactor. The first gas-solid separator is adapted to collect chamberproducts from the drying chamber and separate the chamber products intoa first type of sold particles and waste products.

The first gas-solid separator includes a separator inlet connected tothe chamber outlet and adapted to collect the chamber products from thedrying chamber, a first separator outlet adapted to deliver the firsttype of solid particles, and a second separator outlet adapted todeliver waste products out of the first gas-solid separator. The reactorincludes a reactor inlet connected to the first separator outlet andadapted to receive the first type of solid particles, a gas inletconnected to a second gas line to flow a second gas and form a secondgas-solid mixture inside the reactor, and a reactor outlet. A secondtype of solid particles is obtained from a reaction of the secondgas-solid mixture within the using energy from the second gas that isheated to a reaction temperature.

In one aspect, the system uses heated gas pre-heated to a reactiontemperature and flowed from the second gas line into the reactor asenergy source for reacting the second gas-solid mixture into an oxidizedreaction product within the reactor. In another aspect, the systemprovides a second gas-solid separator connected to the reactor outlet tocollect the oxidized reaction product and separate the oxidized reactionproduct into second type of solid particles and gaseous side products.In still another aspect, one or more cooling fluid lines are providedand adapted to cool the second type of solid particles.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 illustrates one embodiment of a flow chart of a method ofproducing a material for a battery electrochemical cell.

FIG. 2 illustrates a flow chart of various apparatuses that can be usedto perform a process of preparing a battery material according oneembodiment of the invention.

FIG. 3 is a schematic of a process system useful in preparing a materialfor a battery electrochemical cell according another embodiment of theinvention.

FIGS. 4A-4F show schematics of exemplary drying chambers configured inthe process system of FIG. 3 according to various embodiments of theinvention.

FIGS. 5A-5C show schematics of exemplary gas-solid separators connectedto a drying chamber of a process system useful in preparing a materialof a battery cell according various embodiments of the invention.

FIGS. 6A-6D show schematics of exemplary reactors useful in a processsystem of FIG. 3 for preparing a material of a battery cell accordingvarious embodiments of the invention.

DETAILED DESCRIPTION

The present invention generally provides a process system for preparinga material of a battery cell. The process system includes a mistgenerator, a drying chamber, one or more gas-solid separators and areactor. The process system is useful in performing a continuous processto manufacture a material for a battery cell, save materialmanufacturing time and energy, and solve the problems of highmanufacturing cost, low yield, poor quality consistency, low electrodedensity, low energy density as seen in conventional active materialmanufacturing processes.

In one aspect, precursor compounds, such as metal-containing precursorsare mixed into a liquid mixture such that the ratio of different metalprecursors can be adjustable in desirable ratio and still able to obtainuniform blending of the precursors. The liquid mixture is then promptlydried into evenly mixed solid particles, which are continuouslydelivered into a rector to mix with a gas to form a gas-solid mixtureand be reacted in gas phase.

In another aspect, heated air or gas is served as the gas source forforming various gas-solid mixtures and as the energy source forreactions inside the drying chamber and the reactor. In still anotheraspect, the gas-solid mixtures formed inside the drying chamber and/orthe reactor are further separated into solid particles. In oneembodiment, one or more gas-solid separators are used in the processsystem to separate gas-solid mixtures inside the drying chamber intosolid particles, which contain a uniform mixture of metal precursorcompounds in desired ratio, and continuously deliver the mixed solidparticles into the reactor for further reaction. Further, unwanted wasteproducts and reaction side products are separated and removed during thecontinuous material manufacturing process to ensure the quality of finalproduct particles.

Reaction products from the reactor are delivered out of the reactor andcooled down. After cooling, the reaction products contain solid materialparticles or fine powers of an oxidized form of the precursorcomposition (e.g., a metal oxide material, such as fine powers of amixed metal oxide material), with desired crystal structure, particlesize, and morphology. Accordingly, high quality and consistent activebattery materials can be obtained with much less time, labor, andsupervision than materials prepared from conventional manufacturingprocesses.

FIG. 1 illustrates a method 100 of producing a material useful in abattery electrochemical cell. Firstly, at step 110 of the method 100, aliquid mixture is formed from two or more precursors. In general, liquidform of a precursor compound can be prepared directly into a liquidmixture in a desired concentration. Solid form of a precursor compoundcan be dissolved or dispersed in a suitable solvent (e.g., water,alcohol, isopropanol, or any other organic or inorganic solvents, andtheir combinations) to form into a liquid mixture of an aqueoussolution, slurry, gel, aerosol or any other suitable liquid forms. Forexample, desirable molar ratio of two or more solid precursors can beprepared into a liquid mixture, such as by measuring and preparingappropriate amounts of the two or more solid precursors into a containerwith suitable amounts of a solvent. Depending on the solubility of theprecursors in the solvent, pH, temperature, and mechanical stirring andmixing can be adjusted to obtain a liquid mixture where the precursorcompounds are fully dissolved and/or evenly dispersed.

In one example, two or more metal-containing precursors are mixed into aliquid mixture for obtaining a final reaction product of a mixed metaloxide material. Exemplary metal-containing precursors include, but arenot limited to, metal salts, lithium-containing compound,cobalt-containing compound, manganese-containing compound,nickel-containing compound, lithium sulfate (Li₂SO₄), lithium nitrate(LiNO₃), lithium carbonate (Li₂CO₃), lithium acetate (LiCH₂COO), lithiumhydroxide (LiOH), lithium formate (LiCHO₂), lithium chloride (LiCl),cobalt sulfate (CoSO₄), cobalt nitrate (Co(NO₃)₂), cobalt carbonate(CoCO₃), cobalt acetate (Co(CH₂COO)₂), cobalt hydroxide (Co(OH)₂),cobalt formate (Co(CHO₂)₂), cobalt chloride (CoCl₂), manganese sulfate(MnSO₄), manganese nitrate (Mn(NO₃)₂), manganese carbonate (MnCO₃),manganese acetate (Mn(CH₂COO)₂), manganese hydroxide (Mn(OH)₂),manganese formate (Mn(CHO₂)₂), manganese chloride (MnCl₂), nickelsulfate (NiSO₄), nickel nitrate (Ni(NO₃)₂), nickel carbonate (NiCO₃),nickel acetate (Ni(CH₂COO)₂), nickel hydroxide (Ni(OH)₂), nickel formate(Ni(CHO₂)₂), nickel chloride (NiCl₂), aluminum (Al)-containing compound,titanium (Ti)-containing compound, sodium (Na)-containing compound,potassium (K)-containing compound, rubidium (Rb)-containing compound,vanadium (V)-containing compound, cesium (Cs)-containing compound,chromium (Cr)-containing compound, copper (Cu)-containing compound,magnesium (Mg)-containing compound, iron (Fe)-containing compound, andcombinations thereof, among others.

Not wishing to be bound by theory, it is contemplated that, in order toprepare an oxide material with two or more different metals, all of therequired metal elements are first mixed into a liquid mixture (e.g.,into a solution, a slurry, or a gel mixture) using two or moremetal-containing precursor compounds as the sources of each metalelement such that the two or more different metals can be mixeduniformly at desired ratio. As an example, to prepare a liquid mixtureof an aqueous solution, slurry, or gel, one or more metal salts withhigh water solubility can be used. For example, metal nitrate, metalsulfate, metal chloride, metal acetate, metal formate can be used.Organic solvents, such as alcohols, isopropanol, etc., can be used todissolve or disperse metal-containing precursors with low watersolubility. In some cases, the pH value of the liquid mixture can beadjusted to increase the solubility of the one or more precursorcompounds. Optionally, chemical additives, gelation agents, andsurfactants, such as ammonia, EDTA, etc., can be added into the liquidmixture to help dissolve or disperse the precursor compounds in a chosensolvent.

At step 120, a first flow of a first gas is flowed into a dryingchamber. At step 130, a mist of the liquid mixture is generated insidethe drying chamber. The mist may be generated by a mist generator, suchas a nozzle, a sprayer, an atomizer, or any other mist generators. Mostmist generators employ air pressure or other means to covert a liquidsolution, a slurry, or a gel mixture into liquid droplets. The mistgenerator can be coupled to a portion of the drying chamber to generatea mist (e.g., a large collection of small size droplets) of the liquidmixture directly within the drying chamber. As an example, an atomizercan be attached to a portion of the drying chamber to spray or injectthe liquid mixture into a mist containing small sized droplets directlyinside the drying chamber. In general, a mist generator that generates amist of mono-sized droplets is desirable. Alternatively, a mist can begenerated outside the drying chamber and delivered into the dryingchamber.

Desired liquid droplet sizes can be adjusted by adjusting the sizes ofliquid delivery/injection channels within the mist generator. Dropletsize ranging from a few nanometers to a few hundreds of micrometers canbe generated. Suitable droplet sizes can be adjusted according to thechoice of the mist generator used, the precursor compounds, thetemperature of the drying chamber, the flow rate of the first gas, andthe residence time inside the drying chamber. As an example, a mist withliquid droplet sizes between one tenth of a micron and one millimeter isgenerated inside the drying chamber.

Not wishing to be bound by theory, in the method 100 of manufacturing abattery material using two or more precursor compounds, it iscontemplated that the two or more precursor compounds are prepared intoa liquid mixture and then converted into droplets, each droplet willhave the two or more precursors uniformly distributed together. Then,the moisture of the liquid mixture is removed by passing the dropletsthrough the drying chamber and the flow of the first gas is used tocarry the mist within the drying chamber for a suitable residence time.It is further contemplated that the concentrations of the precursorcompounds in a liquid mixture and the droplet sizes of the mist of theliquid mixture can be adjusted to control the chemical composition,particle sizes, and size distribution of final product particles of thebattery material.

At step 140, the mist of the liquid mixture is dried within the dryingchamber for a desired first residence time to remove its moisture. Asthe removal of the moisture from the mist of the precursor compounds isperformed within the drying chamber filled with the first gas, a firstgas-solid mixture composing of the heated first gas and the precursorcompounds is formed. Accordingly, one embodiment of the inventionprovides that the first gas flowed within the drying chamber is used asthe gas source for forming a first gas-solid mixture within the dryingchamber. In another embodiment, the first gas flowed within the dryingchamber is heated and the thermal energy of the heated first gas isserved as the energy source for carrying out drying reaction and otherreactions inside the drying chamber. The first gas can be heated to atemperature of between 70° C. to 600° C. by passing through a suitableheating mechanism, such as electricity powered heater, fuel-burningheater, etc.

In one configuration, the first gas is pre-heated prior to flowing intothe drying chamber. Optionally, drying the mist can be carried out byheating the drying chamber directly, such as heating the chamber body ofthe drying chamber. The advantages of using heated gas are fast heattransfer, high temperature uniformity, and easy to scale up, amongothers. The drying chambers may be any chambers, furnaces with enclosedchamber body, such as a dome type ceramic drying_chamber, a quartzchamber, a tube chamber, etc. Optionally, the chamber body is made ofthermal insulation materials (e.g., ceramics, etc.) to prevent heat lossduring drying.

The first gas may be, for example, air, oxygen, carbon dioxide, nitrogengas, hydrogen gas, inert gas, noble gas, and combinations thereof, amongothers. For example, heated air can be used as an inexpensive gas sourceand energy source for drying the mist. The choice of the first gas maybe a gas that mix well with the mist of the precursors and dry the mistwithout reacting to the precursors. In some cases, the chemicals in thedroplets/mist may react to the first gas and/or to each other to certainextent during drying, depending on the drying temperature and thechemical composition of the precursors. In addition, the residence timeof the mist of thoroughly mixed precursor compounds within the dryingchamber is adjustable and may be, for example, between one second andone hour, depending on the flow rate of the first gas, and the length ofthe path that the mist has to flow through within the drying chamber.

The mist of the liquid mixture is being dried within the drying chamberby flowing the heated first gas continuously and/or at adjustable,variable flow rates. At the same time, the dried solid particles ofprecursors are carried by the first gas, as a thoroughly-mixed gas-solidmixture, through a path within the drying chamber, and as more first gasis flowed in, the gas-solid mixture is delivered out of the dryingchamber and continuously delivered to a gas-solid separator connected tothe drying chamber.

Next, at step 150, the gas-solid mixture comprising of the first gas andthe precursors mixed together are separated into a first type of solidparticles and a waste product using, for example, a gas-solid separator.The first type of solid particles may include thoroughly-mixed solidparticles of the precursors.

At step 160, the first type of solid particles is delivered into areactor to be reacted into reaction products. At step 170, a second flowof a second gas that is heated to a second temperature is flowed insidethe reactor. Accordingly, the heated second gas and the first type ofsolid particles delivered inside the reactor are mixed together to forma second gas-solid mixture. In one embodiment, the second gas is heatedto a desired reaction temperature, such as a temperature of between 400°C. to 1300° C., and flowed into the reactor to serve as the energysource for reacting the precursor-containing first type of solidparticles.

At step 180, the second gas-solid mixture inside the reactor is reactedfor a second residence time into a reaction product. The secondresidence time may be any residence time to carry out a completereaction of the second gas solid mixture, such as a residence time ofbetween one second and ten hours or longer. Reactions of the secondgas-solid mixture within the reactor may include any of oxidation,reduction, decomposition, combination reaction, phase-transformation,re-crystallization, single displacement reaction, double displacementreaction, combustion, isomerization, and combinations thereof. Forexample, the second gas-solid mixture may be oxidized, such as oxidizingthe precursor compounds into an oxide material.

Exemplary second gas include, but are not limited to air, oxygen, carbondioxide, an oxidizing gas, nitrogen gas, inert gas, noble gas, andcombinations thereof. For an oxidation reaction inside the reactor, suchas forming an oxide material from one or more precursors, an oxidizinggas can be used as the second gas. For reduction reactions inside thereactor, a reducing gas can be used as the second gas. As an example,heated air is used as the gas source for forming the second gas-solidmixture.

It is contemplated to obtain a second type of solid particles from areaction of the second gas-solid mixture within the reactor using energyfrom the second gas that is heated to a reaction temperature to fullycomplete the reaction and obtain desired crystal structure of finalreaction products. The advantages of flowing air or gas already heatedare faster heat transfer, uniform temperature distribution (especiallyat high temperature range), and easy to scale up, among others.

At step 190, reaction products (e.g., a gas-solid mixture of oxidizedreaction products mixed with second gas and/or other gas-phaseby-products, or waste products, etc.) are delivered out of the reactorand cooled to obtain final solid particles of desired size, morphology,and crystal structure, ready to be further used for batteryapplications. For example, the reaction product may be slowly cooleddown to room temperature to avoid interfering or destroying a process offorming into its stable energy state with uniform morphology and desiredcrystal structure.

FIG. 2 illustrates a flow chart of incorporating the method 100 ofpreparing a material for a battery electrochemical cell using a system300 fully equipped with all of the required manufacturing tools. Thesystem 300 generally includes a mist generator 306, a drying chamber310, a gas-solid separator 320, and a reactor 340. First, a liquidmixture containing two or more precursors is prepared and delivered intothe mist generator 306 of the system 300. The mist generator 306 iscoupled to the drying chamber 310 and adapted to generate a mist fromthe liquid mixture. A first flow of heated gas can be flowed into thedrying chamber 310 to fill and pre-heat an internal volume of the dryingchamber 310 prior to the formation of the mist or at the same time whenthe mist is generated inside the drying chamber 310. The mist is mixedwith the heated gas and its moisture is removed such that a gas-solidmixture, which contains the first heated gas, two or more precursors,and/or other gas-phase waste product or by-products, etc., is formed.

Next, the gas-solid mixture is continuously delivered into the gas-solidseparator 320 which separates the gas-solid mixture into a first type ofsolid particles and waste products. The first type of solid particles isthen delivered into the reactor 340 to be mixed with a second flow ofheated gas and form a second gas-solid mixture. The reaction inside thereactor is carried out for a reaction time until reaction products canbe obtained. Optionally, the reaction product gas-solid mixture can bedelivered into a second gas-solid separator (e.g., a gas-solid separator328) to separate and obtain final solid product particles and a gaseousside product. In addition, one or more flows of cooling fluids (e.g.,gases or liquids) may be used to cool the temperature of the reactionproducts. The final solid product particles can be delivered out of thesystem 300 for further analysis on their properties (e.g., specificcapacity, power performance, battery charging cycle performance, etc.),particle sizes, morphology, crystal structure, etc., to be used as amaterial in a_battery cell. Finally, the final particles are packed intoa component of a battery cell.

FIG. 3 is a schematic of the system 300, which is one example of anintegrated tool/apparatus that can be used to carry out a fast, simple,continuous and low cost manufacturing process for preparing a materialfor a battery electrochemical cell. The system 300 is connected to aliquid mixer 304, which in turn is connected to two or more reactantsources 302A, 302B. The reactant sources 302A, 302B are provided tostore various precursor compounds and liquid solvents. Desired amountsof precursor compounds (in solid or liquid form) and solvents are dosedand delivered from the reactant sources 302A, 3028 to the liquid mixer304 so that the precursor compounds can be dissolved and/or dispersed inthe solvent and mix well into a liquid mixture. If necessary, the liquidmixer 304 is heated to a temperature, such as between 30° C. and 90° C.to help uniformly dissolve, disperse, and/or mix the precursors. Theliquid mixer 304 is optionally connected to a pump 305, which pumps theliquid mixture from the liquid mixer 304 into the mist generator 306 ofthe system 300 to generate a mist.

The mist generator 306 converts the liquid mixture into a mist withdesired droplet size and size distribution. In addition, the mistgenerator 306 is coupled to the drying chamber 310 in order to dry andremove moisture from the mist and obtain thoroughly-mixed solidprecursor particles. In one embodiment, the mist generator 306 ispositioned near the top of the drying chamber 310 that is positionedvertically (e.g., a dome-type drying chamber, etc.) to inject the mistinto the drying chamber 310 and pass through the drying chambervertically downward. Alternatively, the mist generator can be positionednear the bottom of the drying chamber 310 that is vertically positionedto inject the mist upward into the drying chamber to increase theresidence time of the mist generated therein. In another embodiment,when the drying chamber 310 is positioned horizontally (e.g., a tubedrying chamber, etc.) and the mist generator 306 is positioned near oneend of the drying chamber 310 such that a flow of the mist, beingdelivered from the one end through another end of the drying chamber310, can pass through a path within the drying chamber 310 for thelength of its residence time.

The drying chamber 310 generally includes a chamber inlet 315, a chamberbody 312, and a chamber outlet 317. In one configuration, the mistgenerator 306 is positioned inside the drying chamber 310 near thechamber inlet 315 and connected to a liquid line 303 adapted to flow theliquid mixture therein from the liquid mixer 304. For example, theliquid mixture within the liquid mixer 304 can be pumped by the pump 305through the liquid line 303 connected to the chamber inlet 315 into theinternal volume of the drying chamber 310. Pumping of the liquid mixtureby the pump 305 can be configured, for example, continuously at adesired delivery rate (e.g., adjusted by a metered valve or other means)to achieve good process throughput of system 300. In anotherconfiguration, the mist generator 306 is positioned outside the dryingchamber 310 and the mist generated therefrom is delivered to the dryingchamber 310 via the chamber inlet 315.

One or more gas lines (e.g., first gas lines 331A, 331B, 331C, 331D,etc.) can be coupled to various portions of the drying chamber 310 andadapted to flow a first gas from a gas source 332 into the dryingchamber 310. A flow of the first gas stored in the gas source 332 can bedelivered, concurrently with the formation of the mist inside dryingchamber 310, into the drying chamber 310 to carry the mist through thedrying chamber 310, remove moisture from the mist, and form a gas-solidmixture containing the precursors. Also, the flow of the first gas canbe delivered into the drying chamber 310 prior to the formation of themist to fill and preheat an internal volume of the drying chamber 310prior to generating the mist inside the drying chamber 310.

In one example, the first gas line 331A is connected to the top portionof the drying chamber 310 to deliver the first gas into the mistgenerator 306 positioned near the chamber inlet 315 to be mixed with themist generated by the mist generator 306 inside the drying chamber 310.In one embodiment, the first gas is preheated to a temperature ofbetween 70° C. and 600° C. to mix with and remove moisture from themist.

As another example, the first gas line 331B delivering the first gastherein is connected to the chamber inlet 315 of the drying chamber 310,in close proximity with the liquid line 303 having the liquid mixturetherein. Accordingly, the first gas can thoroughly mix with the mist ofthe liquid mixture inside the drying chamber 310.

In another example, the first gas line 331C is connected to the chamberbody 312 of the drying chamber 310 to deliver the first gas therein andmix the first gas with the mist generated from the mist generator 306.In addition, the first gas line 331D connected to the drying chamber 310near the chamber outlet 317 may be used to ensure the gas-solid mixtureformed within the drying chamber 310 is uniformly mixed with the firstgas.

The flow of the first gas may be pumped through an air filter to removeany particles, droplets, or contaminants, and the flow rate of the firstgas can be adjusted by a valve or other means. In one embodiment, thefirst gas is heated to a drying temperature to mix with the mist andremove moisture from the mist. It is designed to obtain spherical solidparticles from a thoroughly-mixed liquid mixture of two or moreprecursors after drying the mist of the liquid mixture. In contrast,conventional solid-state manufacturing processes involve mixing ormilling a solid mixture of precursor compounds, resulting in unevenmixing of precursors.

FIGS. 4A-4F show examples of the drying chamber 310 configured in thesystem 300 of FIG. 3 according to various embodiments of the invention.Inside the drying chamber 310, there are at least a mist flow 402 and atleast a first gas flow 404 flowing and passing through therein. In oneembodiment, the flows of the mist of the liquid mixture (e.g., the mistflow 402) and the flows of the first gas (e.g., the first gas flow 404)may encounter with each other inside the drying chamber at an angle of 0degree to 180 degrees. In addition, the air streams of the mist flow 402and the first gas flow 404 may be flowed in straight lines, spiral,intertwined, and/or in other manners.

For example, the flow of the first gas and the flow of the mist flowinginside the drying chamber can be configured to flow as co-currents, asshown in the examples of FIGS. 4A-4C and 4F. Advantages of co-currentflows are shorter residence time, lower particle drying temperature, andhigher particle separation efficiency, among others. As another example,the flow of the first gas and the flow of the mist flowing inside thedrying chamber can be configured to flow as counter currents, as shownin the examples of FIG. 4D-4E. Advantage of counter currents are longerresidence time and higher particle drying temperature, among others

In the example of FIG. 4A, the mist flow 402 and the first gas flow 404are configured at an angle of zero (0) degree and can merge into a mixedflow (e.g., co-currents) inside the drying chamber. The first gas flow404 is flowed into a portion of the drying chamber near where the mistflow 402, such that the first gas is in close proximity with the mist toheat and dry the mist.

In the example of FIG. 48, the mist flow 402 and the first gas flow 404are configured at an a angle of less than 90 degree and can merge into amixed flow inside the drying chamber. In the example of FIG. 4C, themist flow 402 and the first gas flow 404 are configured at an a angle of90 degree and can merge into a mixed flow inside the drying chamber. Inaddition, the mist flow 402 and the first gas flow 404 may be flowed atvarious angles directed to each other and/or to the perimeter of thechamber body to promote the formation of spiral, intertwined, and/orother air streams inside the drying chamber 310.

In the example of FIG. 4D, the mist flow 402 and the first gas flow 404are configured at an a angle of 180 degree and are flowed as countercurrents. FIG. 4E illustrates one example of the mist generator 306positioned at the bottom of the drying chamber 310 such that the mistflow 402 and the first gas flow 404 can be configured at an a angle of180 degree and are flowed as counter currents.

In an alternative embodiment, the drying chamber 310 can be positionedhorizontally. Similarly, the mist flow 402 and the first gas flow 404can be configured at an a angle of between 0 degree and 180 degree. Inthe example of FIG. 4F, the mist flow 402 and the first gas flow 404 areconfigured at an angle of zero (0) degree and flowed as co-currents tobe merge into a mixed flow inside the drying chamber 310 along ahorizontal path.

Referring back to FIG. 3, once the mist of the liquid mixture is driedand formed into a gas-solid mixture with the first gas, the gas-solidmixture is delivered out of the drying chamber 310 via the chamberoutlet 317. The drying chamber 310 is coupled to the gas-solid separator320 of the system 300. The gas-solid separator 320 collects chamberproducts (e.g., a gas-solid mixture having the first gas and driedparticles of the two or more precursors mixed together) from the chamberoutlet 317.

The gas-solid separator 320 includes a separator inlet 321A, two or moreseparator outlets 322A, 324A. The separator inlet 321A is connected tothe chamber outlet 317 and adapted to collect the gas-solid mixture andother chamber products from the drying chamber 310. The gas-solidseparator 320 separates the gas-solid mixture from the drying chamber310 into a first type of solid particles and waste products. Theseparator outlet 322A is adapted to deliver the first type of solidparticles to the reactor 340 for further processing and reactions. Theseparator outlet 324A is adapted to deliver waste products out of thegas-solid separator 320.

The waste products may be delivered into a gas abatement device 326A tobe treated and released out of the system 300. The waste product mayinclude, for example, water (H₂O) vapor, organic solvent vapor,nitrogen-containing gas, oxygen-containing gas, O₂, O₃, nitrogen gas(N₂), NO, NO₂, NO₂, N₂O, N₄O, NO₃, N₂O₃, N₂O₄, N₂O₅, N(N₂)₃,carbon-containing gas, carbon dioxide (CO₂), CO, hydrogen-containinggas, H₂, chlorine-containing gas, C₂, sulfur-containing gas, SO₂, smallparticles of the first type of solid particles, small particles of thesecond type of solid particles, and combinations thereof.

The first type of solid particles may include at least particles of thetwo or more precursors that are dried and uniformly mixed together. Itis contemplated to separate the first type of solid particles away fromany side products, gaseous products or waste products, prior to reactingthe two or more precursors in the reactor 340. Accordingly, the system300 is designed to mix the two or more precursors uniformly, dry the twoor more precursors, separate the dried two or more precursors, and reactthe two or more precursors into final reaction products in a continuousmanner.

Suitable gas-solid separators include cyclones, electrostaticseparators, electrostatic precipitators, gravity separators, inertiaseparators, membrane separators, fluidized beds, classifiers, electricsieves, impactors, particles collectors, leaching separators,elutriators, air classifiers, leaching classifiers, and combinationsthereof, among others. Figures SA-5C show examples of gas-solidseparators 320A, 320B, 320C, 3200, being connected to the drying chamber310 of the process system according various embodiments of theinvention.

In the example of FIG. 5A, the gas-solid separator 320A is a cycloneparticle collector. The gas-solid separator 320A collects the gas-solidmixture from the drying chamber 310 via the separator inlet 321A andseparates the gas-solid mixture, through high speed rotational flow,gravity, and other air flows, within its cylindrical and/or conicalbody. Air flows in a helical pattern, beginning at the top (wide end) ofthe gas-solid separator 320A and ending at the bottom (narrow) endbefore exiting the gas-solid separator 320A in a straight stream throughthe center of the cyclone and out the top via the separator outlet 324A.Larger (denser) particles in a rotating stream may strike the outsidewall of the gas-solid separator 320A and then fall to the bottom of thegas-solid separator 320A to be removed via the separator outlet 322A. Ina conical portion of the gas-solid separator gas-solid separator 320A,as the rotating flow moves towards the narrow end of the gas-solidseparator 320A, the rotational radius of the flow of the gas-solidmixture is reduced, thus being able to separate smaller and smallerparticles. Usually, the geometry, together with air flow rate inside thegas-solid separator 320A defines the particle cut point size of thegas-solid separator 320A.

In the example of FIG. 5B, the gas-solid separator 320B is a cycloneparticle collector. The gas-solid separator 3208 is optionally used toensure the gas-solid mixture from the drying chamber 310 is separatedinto specific particle cut point size, to be circulated back into thedrying chamber 310 via the separator outlet 322A. Chamber products fromthe drying chamber 310 are delivered from a chamber outlet 519 into thegas-solid separator 320C. The gas-solid separator 320C may be, forexample, a fluidized bed particle collector, for carrying out dryingand/or multi-phase chemical reactions. A gas is flowed from a gas line515 through a distributor plate within the gas-solid separator 320C todistribute and fill the gas-solid separator 320C. The fluid flowed fromthe gas line 515 is passed, at high enough velocities, through thegas-solid separator 320C full of a granular solid material (e.g., thechamber products, gas-solid mixture, and other particles delivered fromthe drying chamber 310) to suspend the solid material and cause it tobehave as though it were a fluid, a process known as fluidization. Solidparticles supported above the distributor plate can mix well and beseparated from gas, liquid or other waste products, which are deliveredout of the gas-solid separator 320C via a gas outlet 537. Solidparticles of the two or more precursors that are dried and uniformlymixed together are delivered out of the gas-solid separator 320C via aseparator outlet 522.

In the example of FIG. 5C, the gas-solid separator 320D is anelectrostatic precipitating (ESP) particle collector. The gas-solidseparator 320D collect the gas-solid mixture or chamber products fromthe drying chamber 310 and removes solid particles from a flowing gas(such as air) using the force of an induced electrostatic charge withminimal impedance for the flow of gases through the device, an ESPparticle collector applies energy only to the particles being collected(not to any gases or liquids) and therefore is very efficient in energyconsumption. After separation through the gas-solid separator 320D, thefirst type of solid particles are delivered out via the separator outlet322A and the waste products are flowed out via the separator outlet324A.

Referring back to FIG. 3, once the first type of solid particles areseparated and obtained, it is delivered into the reactor 340 for furtherreaction. The reactor 340 includes a gas inlet 333, a reactor inlet 345,and a reactor outlet 347. The reactor inlet 345 is connected to theseparator outlet 322A and adapted to receive the first type of solidparticles. Optionally, a vessel 325 is adapted to store the first typeof solid particles prior to adjusting the amounts of the first type ofsolid particles delivered into the reactor 340.

The gas inlet 333 of the reactor 340 is coupled to a heating mechanism380 to heat a second gas from a gas source 334 to a reaction temperatureof between 400° C. and 1300° C. The heating mechanism 380 can be, forexample, an electric heater, a gas-fueled heater, a burner, among otherheaters. Additional gas lines can be used to deliver heated air or gasinto the reactor 340, if needed. The pre-heated second gas can fill thereactor 340 and maintained the internal temperature of the reactor 340,much better and energy efficient than conventional heating of thechamber body of a reactor.

The second gas flowed inside the reactor 340 is designed to be mixedwith the first type of solid particles and form a second gas-solidmixture inside the reactor 340. Thermal energy from the pre-heatedsecond gas is used as the energy source for reacting the secondgas-solid mixture within the reactor 340 for a residence time of between1 second and ten hours, or longer, depending on the reaction temperatureand the type of the precursors initially delivered into the system 300.The second gas-solid mixture is then go through one or more reactions,including, but not limited to, oxidation, reduction, decomposition,combination reaction, phase-transformation, re-crystallization, singledisplacement reaction, double displacement reaction, combustion,isomerization, and combinations thereof. One embodiment of the inventionprovides the control of the temperature of the reactor 340 by thetemperature of the heated second gas. The use of the heated second gasas the energy source inside the reactor 340 provides the benefits offast heat transfer, precise temperature control, uniform temperaturedistribution therein, and/or easy to scale up, among others.

Once the reactions inside the reactor 340 are complete, for example,upon the formation of desired crystal structure, particle morphology,and particle size, reaction products are delivered out of the reactor340 via the reactor outlet 347 and/or a reactor outlet 618 and cooleddown. The cooled reaction products include a second type of solidparticles containing, for example, oxidized reaction product particlesof the precursor compounds which are suitable as a material of a batterycell.

Optionally, the system 300 includes a second gas-solid separator, suchas a gas-solid separator 328, which collects the reaction products fromthe reactor outlet 347 of the reactor 340. The gas-solid separator 328may be a particle collector, such as cyclone, electrostatic separator,electrostatic precipitator, gravity separator, inertia separator,membrane separator, fluidized beds classifiers electric sieves impactor,leaching separator, elutriator, air classifier, leaching classifier, andcombinations thereof. Suitable examples of the gas-solid separator 328include the exemplary gas-solid separators as shown in FIGS. 5A-5C.

The gas-solid separator 328 of the system 300 generally includes aseparator inlet 321B, a separator outlet 3228 and a separator outlet324B and is used to separate the reaction products into the second typeof solid particles and gaseous side products. The gaseous side productsmay be delivered into a gas abatement device 326B to be treated andreleased out of the system 300. The gaseous side products separated bythe gas-solid separator 328 may generally contain water (H₂O) vapor,organic solvent vapor, nitrogen-containing gas, oxygen-containing gas,O₂, O₃, nitrogen gas (N₂), NO, NO₂, NO₂, N₂O, N₄O, NO₃, N₂O₃, N₂O₄,N₂O₅, N(NO₂)₃, carbon-containing gas, carbon dioxide (CO₂), CO,hydrogen-containing gas, H₂, chlorine-containing gas, Cl₂,sulfur-containing gas, SO₂, small particles of the first type of solidparticles, small particles of the second type of solid particles, andcombinations thereof.

In addition, the system 300 may further include one or more coolingfluid lines 353, 355 connected to the reactor outlet 347 or theseparator outlet 322A of the gas solid separator 328 and adapted to coolthe reaction products and/or the second type of solid particles. Thecooling fluid line 353 is adapted to deliver a cooling fluid (e.g., agas or liquid) from a source 352 to the separator inlet 3218 of thegas-solid separator 328. The cooling fluid line 355 is adapted todeliver a cooling fluid, which may filtered by a filter 354 to removeparticles, into a heat exchanger 350.

The heat exchanger 350 is adapted to collect and cool the second type ofsolid particles and/or reaction products from the gas-solid separator328 and/or the reactor 340 by flowing a cooling fluid through them. Thecooling fluid has a temperature lower than the temperature of thereaction products and the second type of solid particles delivered fromthe gas-solid separator 328 and/or the reactor 340. The cooling fluidmay have a temperature of between 4° C. and 30° C. The cooling fluid maybe liquid water, liquid nitrogen, an air, an inert gas or any other gaswhich would not react to the reaction products.

FIGS. 6A-6D illustrates examples of reactors 340A, 3408, 340C, 340Dwhich can be used in the process 200 and the system 300 for preparing amaterial of a battery cell. In general, the reactor 340 of the system300 can be a fluidized bed reactor, such as a circulating fluidized bedreactor, a bubbling fluidized bed reactor, an annular fluidized bedreactor, a flash fluidized bed reactor, and combinations thereof. Inaddition, the reactor 340 can be any of a furnace-type reactor, such asa rotary furnace, a stirring furnace, a furnace with multipletemperature zones, and combinations thereof.

In the example of FIG. 6A, the reactor 340A is a circulating-typefluidized bed reactor. The reactor 340A receives the first type of solidparticles from the reactor inlet 345 and mixes it with a flow ofpre-heated second gas from the gas line 333 to form a gas-solid mixturewithin the internal volume of the reactor 340A. The gas-solid mixture isheated by the thermal energy of the preheated second gas and completereaction is enhanced by continuously flowing the gas-solid mixture outof the reactor 340A into a gas-solid separator 620 coupled to thereactor 340A. The gas-solid separator 620 is provided to remove sideproducts (and/or a portion of reaction products) out of the system 300via a separator outlet 602 and recirculating solid particles back intothe reactor 340A via a separator outlet 604. Product particles withdesired sizes, crystal structures, and morphology are collected anddelivered out of the gas-solid separator 620 via a separator outlet 618(and/or the separator outlet 602).

In the example of FIG. 6B, the reactor 340B is a bubbling-type fluidizedbed reactor. A flow of pre-heated second gas from the gas line 333 isdelivered into the reactor 340B and passes through a porous medium 628to mix with the first type of solid particles delivered from the reactorinlet 345 and generate a bubbling gaseous fluid-solid mixture within theinternal volume of the reactor 3408. The bubbling gas-solid mixture isheated by the thermal energy of the preheated second gas and completereaction is enhanced by bubbling flows within the reactor 3408. Uponcomplete reaction, gaseous side products are removed out of the reactor340B via the rector outlet 347. Product particles with desired crystalstructures, morphology, and sizes are collected and delivered out of thereactor 3408 via the reactor outlet 618.

In the example of FIG. 6C, the reactor 340C is an annular-type fluidizedbed reactor. A flow of pre-heated second gas from the gas line 333 isdelivered into the reactor 340C and also diverted into additional gasflows, such as gas flows 633, to encourage thorough-mixing of the heatedgas with the solid particles delivered from the reactor inlet 345 andgenerate an uniformly mixed gas-solid mixture within the internal volumeof the reactor 340C. Upon complete reaction, gaseous side products areremoved out of the reactor 340C via the rector outlet 347. Productparticles with desired crystal structures, morphology, and sizes arecollected and delivered out of the reactor 340C via the reactor outlet618.

In the example of FIG. 6D, the reactor 340D is a flash-type fluidizedbed reactor. The reactor 340D receives the solid particles from thereactor inlet 345 and mixes it with a flow of pre-heated gas from thegas line 333 to form a gas-solid mixture. The gas-solid mixture ispassed through a tube reactor body 660 which is coupled to the reactor340D. The gas-solid mixture has to go through the long internal path,which encourages complete reaction using the thermal energy of theheated gas. Gaseous side products are then removed out of the reactor340D via the rector outlet 347, and product particles with desiredcrystal structures, morphology, and sizes are collected and deliveredout of the reactor 340D via the reactor outlet 618. It is noted thatadditional gas lines can be used to deliver heating or cooling air orgas into the reactors 340A, 340B, 340C, 340D.

Referring back to FIG. 3, final reaction products are collected andcooled by one or more separators, cooling fluid lines, and/or heatexchangers, and once cooled, the second type of solid particles aredelivered out of the system 300 and collected in a final productcollector 368. The second type of solid particles may include oxidizedform of precursors, such as an oxide material, suitable to be packedinto a battery cell 370. Additional pumps may also be installed toachieve the desired pressure gradient.

A process control system 390 can be coupled to the system 300 at variouslocations to automatically control the manufacturing process performedby the system 300 and adjust various process parameters (e.g., flowrate, mixture ratio, temperature, residence time, etc.) within thesystem 300. For example, the flow rate of the liquid mixture into thesystem 300 can be adjusted near the reactant sources 302A, 302B, theliquid mixer 304, or the pump 305. As another example, the droplet sizeand generation rate of the mist generated by the mist generator 306 canbe adjusted. In addition, flow rate and temperature of various gasesflowed within the gas lines 331A, 3318, 331C, 331D, 333, 353, 355, 515,etc., can be controlled by the process control system 390. In addition,the process control system 390 is adapted to control the temperature andthe residence time of various gas-solid mixture and solid particles atdesired level at various locations.

Accordingly, a continuous process for producing a material of a batterycell using a system having a mist generator, a drying chamber, one ormore gas-solid separators and a reactor is provided. A mist generatedfrom a liquid mixture of two or more metal precursor compounds indesired ratio is mixed with air and dried inside the drying chamber,thereby forming gas-solid mixtures. One or more gas-solid separators areused in the system to separate the gas-solid mixtures from the dryingchamber into solid particles packed with the two or more metalprecursors and continuously deliver the solid particles into the reactorfor further reaction to obtain final solid material particles withdesired ratio of two or more intercalated metals.

In one embodiment, preparation and manufacturing of a metal oxidematerial is provided. Depending on the details and ratios of the metalprecursor compounds that are delivered into the system 300, theresulting final solid material particles obtained from the system 300may be a metal oxide material, a doped metal oxide material, aninorganic metal salts, among others. Exemplary metal oxide materialsinclude, but are not limited to, titanium oxide (Ti_(x)O_(y), such asTi₂O₅), chromium oxide (Cr_(x)O_(y), such as Cr₂O₇), tin oxide(Sn_(x)O_(y), such as SnO₂, SnO, SnSiO₃, etc.), copper oxide(Cu_(x)O_(y), such as CuO, Cu₂O, etc), aluminum oxide (Al_(x)O_(y), suchas Al₂O₃,), manganese oxide (Mn_(x)O_(y)), iron oxide (Fe_(x)O_(y), suchas Fe₂O₃, etc), among others.

For mixed metal oxide materials, it is desired to control thecomposition of a final reaction product material by the ratio of theprecursor compounds added in a liquid mixture added to the system 300.In one embodiment, a metal oxide with two or more metals(Me_(x)Me′_(y)O_(z)) is obtained. Examples include lithium transitionalmetal oxide (LiMeO₂), lithium titanium oxide (e.g., Li₄Ti₅O₁₂), lithiumcobalt oxide (e.g., LiCoO₂), lithium manganese oxide (e.g., LiMn₂O₄),lithium nickel oxide (e.g., LiNiO₂), lithium iron phosphate (e.g.,LiFePO₄), lithium cobalt phosphate (e.g., LiCoPO₄), lithium manganesephosphate (e.g., LiMnPO₄), lithium nickel phosphate (e.g., LiNiPO₄),sodium iron oxide (e.g., NaFe₂O₃), sodium iron phosphate (e.g.,NaFeP₂O₇), among others.

In another example, a metal oxide with three or four intercalated metalsis obtained. Exemplary metal oxide materials include, but are notlimited to, lithium nickel cobalt oxide (e.g., Li_(x)Ni_(y)Co_(z)O₂),lithium nickel manganese oxide (e.g., Li_(x)Ni_(y)Mn_(z)O₂,Li_(x)Ni_(y)Mn₂O₄, etc.), lithium nickel manganese cobalt oxide (e.g.,Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered structures or layered-layeredstructures; and/or LiNi_(x)Mn_(y)Co_(z)O₂, a NMC oxide material wherex+y+z=1, such as LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.5)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.102), etc.; and/or a mixed metal oxide withdoped metal, among others. Other examples include lithium cobaltaluminum oxide (e.g., Li_(x)Co_(y)Al_(z)O_(n)), lithium nickel cobaltaluminum oxide (e.g., Li_(x)Ni_(y)Co_(z)Al_(a)O_(b)), sodium ironmanganese oxide (e.g., Na_(x)Fe_(y)Mn_(z)O₂), among others. In anotherexample, a mixed metal oxide with doped metal is obtained; for example.Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b) (where Me=doped metal of Al, Mg, Fe,Ti, Cr, Zr, or C), Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b)F_(c) (whereMe=doped metal of Al, Mg, Fe, Ti, Cr, Zr, or C), among others.

Other metal oxide materials containing one or more lithium (Li), nickel(Ni), manganese (Mn), cobalt (Co), aluminum (Al), titanium (Ti), sodium(Na), potassium (K), rubidium (Rb), vanadium (V), cesium (Cs), copper(Cu), magnesium (Mg), iron (Fe), among others, can also be obtained. Inaddition, the metal oxide materials can exhibit a crystal structure ofmetals in the shape of layered, spinel, olivine, etc. In addition, themorphology of the final reaction particles (such as the second type ofsolid particles prepared using the method 100 and the system 300 asdescribed herein) exists as desired solid powders. The particle sizes ofthe solid powders range between 10 nm and 100 um.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed:
 1. A material of a battery cell, comprising: one ormore final solid particles of a reaction product, wherein the reactionproduct is obtained from: forming a gas-solid mixture from one or moreflows of a gas and one or more solid particles of an oxide material withtwo or more metals inside a reaction chamber; reacting the gas-solidmixture inside the reaction chamber; and oxidizing the gas-solid mixtureinto the reaction product, wherein the one or more solid particles ofthe oxide material with two or more metals are obtained from drying amixture formed from one or more gases and a mist of a liquid mixtureinside a drying chamber.
 2. The material of claim 1, wherein the one ormore final solid particles comprise an oxide compound with two or moremetals comprising lithium (Li), and a metal selected from the groupconsisting of cobalt (Co), manganese (Mn), nickel (Ni), aluminum (Al),magnesium (Mg), titanium (Ti), sodium (Na), potassium (K), rubidium(Rb), vanadium (V), cesium (Cs), chromium (Cr), copper (Cu), iron (Fe),and combinations thereof.
 3. The material of claim 1, wherein the one ormore final solid particles comprise a material selected from the groupconsisting of a metal oxide, titanium oxide, chromium oxide, tin oxide,copper oxide, aluminum oxide, manganese oxide, iron oxide, a metal oxidewith two or more metals, lithium transitional metal oxides, lithiumtitanium oxide, lithium cobalt oxide, lithium manganese oxide, lithiumnickel oxide, lithium iron phosphate, lithium cobalt phosphate, lithiummanganese phosphate, lithium nickel phosphate, sodium iron oxide, sodiumiron phosphate, a metal oxide with three or four intercalated metals,lithium nickel cobalt oxide, lithium nickel manganese oxide, lithiumnickel manganese cobalt oxide, Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layeredstructures, Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered-layered structures,LiNi_(x)Mn_(y)Co_(z)O₂ (where x+y+z=1), LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.5)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂, a mixed metal oxide with doped metal,Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b) (where Me=doped metal of Al, Mg, Fe,Ti, Cr, Zr, or C), Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b)F_(c) (whereMe=doped metal of Al, Mg, Fe, Ti, Cr, Zr, or C), lithium cobalt aluminumoxide, lithium nickel cobalt aluminum oxide, sodium iron manganeseoxide, and combinations thereof.
 4. The material of claim 1, wherein theone or more final solid particles are obtained from separating thereaction product into the one or more final solid particles and agaseous side product using one or more separators selected from thegroup consisting of cyclones, electrostatic separators, electrostaticprecipitators, gravity separators, inertia separators, membraneseparators, fluidized beds, classifiers, electric sieves, impactors,particles collectors, leaching separators, elutriators, air classifiers,leaching classifiers, and combination thereof.
 5. The material of claim1, wherein the liquid mixture is selected from the group consisting of asolution of two or more metal-containing precursors, a slurry ofmetal-containing precursors, a gel mixture of metal-containingprecursors, and combinations thereof.
 6. The material of claim 5,wherein the metal-containing precursor comprises a metal-containingcompound selected from the group consisting of metal salts,lithium-containing compound, cobalt-containing compound,manganese-containing compound, nickel-containing compound, lithiumsulfate (Li₂SO₄), lithium nitrate (LiNO₃), lithium carbonate (Li₂CO),lithium acetate (LiCH₂COO), lithium hydroxide (LiOH), lithium formate(LiCHO₂), lithium chloride (LiCl), cobalt sulfate (CoSO₄), cobaltnitrate (Co(NO₃)₂), cobalt carbonate (CoCO₃), cobalt acetate(Co(CH₂COO)₂), cobalt hydroxide (Co(OH)₂), cobalt formate (Co(CHO₂)₂),cobalt chloride (CoCl₂), manganese sulfate (MnSO₄), manganese nitrate(Mn(NO₃)₂), manganese carbonate (MnCO₃), manganese acetate(Mn(CH₂COO)₂), manganese hydroxide (Mn(OH)₂), manganese formate(Mn(CHO₂)₂), manganese chloride (MnCl₂), nickel sulfate (NiSO₄), nickelnitrate (Ni(NO₃)₂), nickel carbonate (NiCO₃), nickel acetate(Ni(CH₂COO)₂), nickel hydroxide (Ni(OH)₂), nickel formate (Ni(CHO₂)₂),nickel chloride (NiCl₂), aluminum (Al)-containing compound, titanium(Ti)-containing compound, sodium (Na)-containing compound, potassium(K)-containing compound, rubidium (Rb)-containing compound, vanadium(V)-containing compound, cesium (Cs)-containing compound, chromium(Cr)-containing compound, copper (Cu)-containing compound, magnesium(Mg)-containing compound, iron (Fe)-containing compound, andcombinations thereof.
 7. The material of claim 1, wherein the one ormore gases inside the drying chamber are heated to a first temperatureand the one or more gases inside the reaction chamber is heated to asecond temperature, and wherein the second temperature is higher thanthe first temperature.
 8. The material of claim 1, wherein the mixtureof the one or more gases and the mist comprises a gas selected from thegroup consisting of air, oxygen, carbon dioxide, nitrogen gas, inertgas, noble gas, and combinations thereof and the gas is heated to atemperature of between 70° C. and 600° C.
 9. The material of claim 1,wherein the one or more flows of the gas comprise a gas selected fromthe group consisting of air, oxygen, carbon dioxide, an oxidizing gas,nitrogen gas, inert gas, noble gas, and combinations thereof and the gasis heated to a temperature of between 400° C. and 1300° C.
 10. Thematerial of claim 1, wherein the mist is generated at desired liquiddroplet sizes of between one tenth of a micron and one millimeter.
 11. Amaterial of a battery electrochemical cell, comprising: one or morefinal solid particles of a reaction product, wherein the reactionproduct is obtained from: flowing one or more flows of a gas into areaction chamber; forming a gas-solid mixture from the one or more flowsof the gas and one or more solid particles of an oxide material with twoor more metals inside the reaction chamber; reacting the gas-solidmixture inside the reaction chamber; and oxidizing the gas-solid mixtureinto the reaction product, wherein the oxide material with two or moremetals is obtained from a process comprising: forming a liquid mixturefrom two or more metal-containing precursors; delivering the liquidmixture into a drying chamber; flowing one or more gases into the dryingchamber; generating a mist of desired liquid droplet sizes from theliquid mixture; forming a mixture from one or more gases and the mist;and drying and reacting the mixture of the one or more gases and themist inside the drying chamber.
 12. The material of claim 11, whereinthe one or more final solid particles of the reaction product comprisean oxide compound with two or more metals comprising lithium (Li), and ametal selected from the group consisting of cobalt (Co), manganese (Mn),nickel (Ni), aluminum (Al), magnesium (Mg), titanium (Ti), sodium (Na),potassium (K), rubidium (Rb), vanadium (V), cesium (Cs), chromium (Cr),copper (Cu), iron (Fe), and combinations thereof.
 13. The material ofclaim 11, wherein the one or more final solid particles comprise amaterial selected from the group consisting of a metal oxide, titaniumoxide, chromium oxide, tin oxide, copper oxide, aluminum oxide,manganese oxide, iron oxide, a metal oxide with two or more metalslithium transitional metal oxides, lithium titanium oxide, lithiumcobalt oxide, lithium manganese oxide, lithium nickel oxide, lithiumiron phosphate, lithium cobalt phosphate, lithium manganese phosphate,lithium nickel phosphate, sodium iron oxide, sodium iron phosphate, ametal oxide with three or four intercalated metals, lithium nickelcobalt oxide, lithium nickel manganese oxide, lithium nickel manganesecobalt oxide, Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered structures,Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered-layered structures,LiNi_(x)Mn_(y)Co_(z)O₂ (where x+y+z=1), LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂, a mixed metal oxide with doped metal,Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b) (where Me=doped metal of Al, Mg, Fe,Ti, Cr, Zr, or C), Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b)F_(c) (whereMe=doped metal of Al, Mg, Fe, Ti, Cr, Zr, or C), lithium cobalt aluminumoxide, lithium nickel cobalt aluminum oxide, sodium iron manganeseoxide, and combinations thereof.
 14. The material of claim 11, whereinthe mist is generated at the desired liquid droplet sizes of between onetenth of a micron and one millimeter, and wherein the liquid mixture isselected from the group consisting of a solution of two or moremetal-containing precursors, a slurry of metal-containing precursors, agel mixture of metal-containing precursors, and combinations thereof.15. The material of claim 14, wherein the metal-containing precursorcomprises a metal-containing compound selected from the group consistingof metal salts, lithium-containing compound, cobalt-containing compound,manganese-containing compound, nickel-containing compound, lithiumsulfate (Li₂SO₄), lithium nitrate (LiNO₃), lithium carbonate (Li₂CO₃),lithium acetate (LiCH₂COO), lithium hydroxide (LiOH), lithium formate(LiCHO₂), lithium chloride (LiCl), cobalt sulfate (CoSO₄), cobaltnitrate (Co(NO₃)₂), cobalt carbonate (CoCO₃), cobalt acetate(Co(CH₂COO)₂), cobalt hydroxide (Co(OH)₂), cobalt formate (Co(CHO₂)₂),cobalt chloride (CoCl₂), manganese sulfate (MnSO₄), manganese nitrate(Mn(NO₃)₂), manganese carbonate (MnCO₃), manganese acetate(Mn(CH₂COO)₂), manganese hydroxide (Mn(OH)₂), manganese formate(Mn(CHO₂)₂), manganese chloride (MnCl₂), nickel sulfate (NiSO₄), nickelnitrate (Ni(NO₃)₂), nickel carbonate (NiCO₃), nickel acetate(Ni(CH₂COO)₂), nickel hydroxide (Ni(OH)₂), nickel formate (Ni(CHO₂)₂),nickel chloride (NiCl₂), aluminum (Al)-containing compound, titanium(Ti)-containing compound, sodium (Na)-containing compound, potassium(K)-containing compound, rubidium (Rb)-containing compound, vanadium(V)-containing compound, cesium (Cs)-containing compound, chromium(Cr)-containing compound, copper (Cu)-containing compound, magnesium(Mg)-containing compound, iron (Fe)-containing compound, andcombinations thereof.
 16. A material of a battery cell, comprising: oneor more final solid particles of an oxidized reaction product, whereinthe oxidized reaction product is obtained from: flowing one or moreflows of a gas into a reaction chamber; forming a gas-solid mixture fromthe one or more flows of the gas and one or more solid particles of anoxide material with two or more metals inside the reaction chamber;reacting the gas-solid mixture inside the reaction chamber; andoxidizing the gas-solid mixture into the oxidized reaction product for aoxidizing residence time period, wherein the oxide material with two ormore metals is obtained from a process comprising: forming a liquidmixture from two or more metal-containing precursors; delivering theliquid mixture into a drying chamber; flowing one or more gases into thedrying chamber; generating a mist of desired liquid droplet sizes fromthe liquid mixture; forming a mixture from one or more gases and themist; and drying and reacting the mixture of the one or more gases andthe mist inside the drying chamber for a drying time period; obtaining adried mixture from the drying chamber; and separating the dried mixtureinto a gaseous side product and the one or more solid particles of theoxide material with two or more metals.
 17. The material of claim 16,wherein the one or more final solid particles of the oxidized reactionproduct comprise an oxide compound with two or more metals comprisinglithium (Li), and a metal selected from the group consisting of cobalt(Co), manganese (Mn), nickel (Ni), aluminum (Al), magnesium (Mg),titanium (Ti), sodium (Na), potassium (K), rubidium (Rb), vanadium (V),cesium (Cs), chromium (Cr), copper (Cu), iron (Fe), and combinationsthereof.
 18. The material of claim 16, wherein the final solid particlescomprise a material selected from the group consisting of a metal oxide,titanium oxide, chromium oxide, tin oxide, copper oxide, aluminum oxide,manganese oxide, iron oxide, a metal oxide with two or more metals,lithium transitional metal oxides, lithium titanium oxide, lithiumcobalt oxide, lithium manganese oxide, lithium nickel oxide, lithiumiron phosphate, lithium cobalt phosphate, lithium manganese phosphate,lithium nickel phosphate, sodium iron oxide, sodium iron phosphate, ametal oxide with three or four intercalated metals, lithium nickelcobalt oxide, lithium nickel manganese oxide, lithium nickel manganesecobalt oxide, Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered structures,Li_(a)Ni_(b)Mn_(c)Co_(d)O_(e) in layered-layered structures,LiNi_(x)Mn_(y)Co_(z)O₂ (where x+y+z=1), LiNi_(0.33)Mn_(0.33)Co_(0.33)O₂,LiNi_(0.6)Mn_(0.2)Co_(0.2)O₂, LiNi_(0.5)Mn_(0.3)Co_(0.2)O₂,LiNi_(0.4)Mn_(0.4)Co_(0.2)O₂, LiNi_(0.7)Mn_(0.15)Co_(0.15)O₂,LiNi_(0.8)Mn_(0.1)Co_(0.1)O₂, a mixed metal oxide with doped metal,Li(Ni_(x)Mn_(y)Co_(z))MeO_(b) (where Me=doped metal of Al, Mg, Fe, Ti,Cr, Zr, or C), Li_(a)(Ni_(x)Mn_(y)Co_(z))MeO_(b)F_(c) (where Me=dopedmetal of Al, Mg, Fe, Ti, Cr, Zr, or C), lithium cobalt aluminum oxide,lithium nickel cobalt aluminum oxide, sodium iron manganese oxide, andcombinations thereof.
 19. The material of claim 16, wherein the mist isgenerated at the desired liquid droplet sizes of between one tenth of amicron and one millimeter, and wherein the liquid mixture is selectedfrom the group consisting of a solution of two or more metal-containingprecursors, a slurry of metal-containing precursors, a gel mixture ofmetal-containing precursors, and combinations thereof.
 20. The materialof claim 16, wherein the metal-containing precursor comprises ametal-containing compound selected from the group consisting of metalsalts, lithium-containing compound, cobalt-containing compound,manganese-containing compound, nickel-containing compound, lithiumsulfate (Li₂SO₄), lithium nitrate (LiNO₃), lithium carbonate (Li₂CO₃),lithium acetate (LiCH₂COO), lithium hydroxide (LiOH), lithium formate(LiCHO₂), lithium chloride (UCI), cobalt sulfate (CoSO₄), cobalt nitrate(Co(NO₃)₂), cobalt carbonate (CoCO₃), cobalt acetate (Co(CH₂COO)₂),cobalt hydroxide (Co(OH)₂), cobalt formate (Co(CHO₂)₂), cobalt chloride(CoCl₂), manganese sulfate (MnSO₄), manganese nitrate (Mn(NO₃)₂),manganese carbonate (MnCO₃), manganese acetate (Mn(CH₂COO)₂), manganesehydroxide (Mn(OH)₂), manganese formate (Mn(CHO₂)₂), manganese chloride(MnCl₂), nickel sulfate (NiSO₄), nickel nitrate (Ni(NO₃)₂), nickelcarbonate (NiCO₃), nickel acetate (Ni(CH₂COO)₂), nickel hydroxide(Ni(OH)₂), nickel formate (Ni(CHO₂)₂), nickel chloride (NiCl₂), aluminum(Al)-containing compound, titanium (Ti)-containing compound, sodium(Na)-containing compound, potassium (K)-containing compound, rubidium(Rb)-containing compound, vanadium (V)-containing compound, cesium(Cs)-containing compound, chromium (Cr)-containing compound, copper(Cu)-containing compound, magnesium (Mg)-containing compound, iron(Fe)-containing compound, and combinations thereof.